Resinous condensates from polyamines and aldehydo-carboxylic acids



Patented Nov. 29, 1949 UNITED STATES ATENT OFFICE RESINOUS CONDENSATES FROM POLY- AMINES AND ALDEHYDO-CARBOXYLIC ACIDS Herman A. Bruson, Rydal, and Warren D. Niederhauser, Philadelphia, Pa., assignors, by mesne assignments, to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application February 21, 1946, Serial No. 649,391

8 Claims.

duction of a new type of resinous condensate, the

provision of resins useful in coating compositions, and useful for laminating paper, cloth, wood, glass, or other materials, and the provision of resins useful in conjunction with fiber-forming materials. It is also an object to provide resins free 'from acidity. Y

We have found that resins meeting a great range of such requirements and useful for a large variety 'of'these and other applications are obtained by reacting by heating together a monoaldehydo- 'monocarboxylic acid, in which the --CH0 group and the COOH group are separated by at least two aliphatic carbon atoms, or an ester thereof,

in which the alcohol portion may be displaced during the reaction, and a polyamine which contains a primary amino group and another amino group which is secondary or primary, the nitrogen atoms of these amine groups being separated by at least four intervening atoms. It is desirable to ensure production of the types of resins here contemplated that there be available for reaction with the aldehyde group in the monocarboxylic acid or ester thereof about one equivalent of a primary aminogroup in the polyamine. shouldalso. be present a second primary or a secondary amine group in a proportion which is about equivalent to the carboxylic acid or ester function.

V Aldehydo-carboxylic acids which meet the requirements of this invention are those in which an open or aliphatic chain of at least two carbon atoms occurs between the aldehyde group and the carboxyl group. These acids may be, therefore,

boxylic acids of importance may be represented by the formula OHCCnH2n-COOH, wherein CnHZn is an alkylene group, straight or branched, of at least two carbon atoms in length and n is an integer having a value of at least two, varying usually from two to sixteen.

There interest. 1 The resins 2 The straight-chained aldehyde-acids may be summarized by the formula wherein n is an integer of at least two. Representative of these are omega-aldehydo-propionic acid, omega-aldehydo-butyric acid, omega-aldehydo-valeric acid, omega-aldehydo-octoic acid. In place of these specific acids, there may be used the various homologues.

Another important group of acids comprises branch-chained aldehyde-acids which have the general formula wherein R is hydrogen or an alkyl group and R is an aliphatic hydrocarbon group. This group may be saturated or unsaturated. Typical aldehydo-acids coming within this formula are [i-carboxy-ethyl diethyl acetaldehyde,

OHCC (C2H5) 2CH2CH2COOH or p-carboxy-ethyl ethyl butyl acetaldehyde,

OHCC (CzHs) (C4H9) CHzCI-IzCOOI-I or. s-carboxyethyl ethyl butenyl-l acetaldehyde, OHCC(C2H5) (CH=CHC2H5)CH2CH2COOH, or {3- carboxyethyl dimethyl acetaldehyde,

or homologues thereof, including those described in United States Patent No. 2,342,607, issued February 22, 1944. From aldehyde-acids of this type resins may be prepared with rather unique properties due, evidently, to the branched-chain structure.

In another useful class of aldehydo-monocarboxylic acids and esters which meet the requirements of this invention are alicyclicaliphatic compounds such as. are formed by the addition of acrolein or crotonaldehyde to aliphatic carboxylic acids or esters having a conjugate diolefinic linkage, such as eleostearic or licanic acids, or the esters thereof. Aldehydo-monocarboxylic acids and esters of this type are described in application Serial No. 623,442, filed October 19, 1945, now abandoned. Resins prepared from polyamines and these acids differ in some respects from resins obtained from the classes of acids described above, being generally softer and having solubilities in a greater variety of solvents. They are highly effective as resinous, non-volatile, non-migrating softeners for other resinous materials.

Instead of the free acids described above, there may be used simple esters of these acids with the lower aliphatic alcohols. When the carboxyl group reacts with an amine group, the alcohol group isdisplaced and can be volatilized from .the resin being formed. Esters of methyl, ethyl, propyl, and butyl alcohol are particularly suscep-i tible to the resin formation herein described,.yet esters of other lower aliphatic alcohols, :such .as hexyl or Z-ethyl hexyl, may be used with the same end effect. Thus, there may be used esters of aldehydo non-aromatic carboxylic acids and: of any lower aliphatic saturated alcohol.

The polyamines which may be used may be classified on the basis of the number of hydrogenbearing nitrogen atoms into twoigroupsu-diamines and polyamines of a functionality greater than two. When linear-type polymers are desired, the diamines having one primary amino group and an amino group which is primary orisecondary are \I used. When other types of resins are'desired, triamines, tetramines, or other higherpolyamines may be used.

Alkylene primary diamines form .a group .of particular importance. These may be designated by the formula NH2-CnH2nNH2, wherein CnH2n is an alkylene chain of at least vfour carbon atoms and n is an integer of at least four, usually varying from four to ten. Typical of these diamines are tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, nonamethylenediamine, and decamethylenediamine.

Related to these diamines are arylaliphatic diamines of the formula NI'I2C6H4(CH2)I1NH2,

where n is anintegerof 1,2, 3,4, 5, etc., there being at least four carbonatoms between the two amino groups in any of the diamines of this general formula which may betakerr for reaction with an aldehydo-carboxylic acid according to this invention. Also, diamines such. as:

NH2(CH2)3 1 (CH2) a H2 may be used.

Aromatic diamines form "another important group of amines, typical o'fwhichare NH2C6H4NH2 and NH2CsH4CeH4NI-I2 In the case of these diamines as with all of .the

diamines described theremust'be at least four carbon atoms between amino groups. This'rule excludespossible isomers of the formulas just given which do not meet this prescribed'requirement. Other useful diamines containingcycles include lA-diaminocyclohexane and its homologuesand also diamines such as:

In cases in "which the final resin is 'to be in-*- soluble and cross-linked; there may be used amines of higherfunctionality than two, such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and thelike, or N,N-d-i'- aminoethylene propylenediamine,

or other polyamines of: amine. functionality greater than two. In these compounds, the more reactive amino groups are separated by chains of at least four carbon atoms with interruption of the carbon chainby nitrogem.

The resins of this invention are 'formed by mixing one or more aldehydo-monocarboxylic .acids or esters thereof, as defined above, with one or more polyamines meeting the requirements shown above and heating the resulting mixture. Volatile products, such as water or alcohol (from esters) are driven-'ofi. The temperature is car- .ried to 200to 300C. preferably with an inert atmosphere and/or with reduced pressure. An inertgas such ashydrogen or nitrogen may be bubbled through the reaction mixture. Ad-

vantageously, the resins are heated in the final stage of preparation in high vacuum to remove volatile matter and to carry the polymers, particularly when linear, to very high molecular weights. If desired, the reaction may be initiated in:a solvent, which is removedrwhenzresins of higher molecular weight are desired.

Resins rangingfrom soluble andxiusiblestodn soluble and infusible may begprepared ;aas;di;- rected. Resinsmay be preparediinaafusible state and rendered insoluble andinfusibleon .further heating. Resins may be'made which "are rubbery and tough to resins which 'arerhard and brittle. These and other properties can bevaried' by choice of reactants, chain length ofreactants, and the extent or degree to which polymerization is carried. Long-chained aliphatic polyamines produce softer,tougher.- resins than cyclic amines. Long chained aldehydomonocarboxylic acids alsopromotetoughness, .andthe short-chained acids tend to .give hardenresins. Some resins from suitable diaminesandalde hydo-carboxylic acids yield fibersor may berolled into foils. Amost interestingpropertymf .the resins of this invention is theincompatibilitywith linear polyamines, polyesters-andpolyurethanes which areiplasticized therewith.

This inventionis .illustratedby theifollowing examples.

-Emampte 51 A mixture-of 8.'60 grams -ofZp 'carboxyethyl-i2' ethylbutyraldehyde.

and 5.80 grams of 'hexamethylene diaminewas heated three hours atl00150 C.'in.an'atmos-' phere of nitrogen. The reaction-vessel was'then I evacuated and heated for three hours at 2 10 260" 'C./1 mm. The product wasan amber-colored elastic resin. It was-solublein'-xylenoland in acetic acid but was insoluble 'in ethanol, butanol, and ethylene dichloride.

. Example 2 ,Example. 3.

A mixture of five partsof decamethylene iik amine and five parts of c-carboxyethyl-z-ethylbutyraldehyde was heated for three and one-half hours at 240-260 C. in an atmosphere of nitrogen and then for seven more hours at the same temperature under a vacuum of 3 mm. The product was a light yellow, elastic, thermoplastic resin which, when warm, could be drawn into filaments.

Example 4 Example 5 To a solution of five parts of B-carboxyethyl-2 ethylbutyraldehyde in thirty parts of petroleum ether, there was added five parts of decamethylenediamine. The mixture was heated and stirred for four hours on the steam bath under reflux. The petroleum ether layer was then decanted off and the brown residual syrup was heated for three hours at 210-220 C./5 mm. while a slow stream of nitrogen was passed through the melt by means of a capillary tube. The produce was an amber elastic resin which could be drawn into filaments. It was soluble in xylenol and in acetic acid but insouble in alcohol, ethylene dichloride, toluene, and in a chloroform-methanol solution.

Example 6 A mixture of 8.6 parts of decamethylenediamine and 9.9 parts or 2-carboxyethyl-2-ethylhexen- 3-al was heated while a slow stream of nitrogen was bubbled through it by means of a capillary tube. The reaction temperature was held at 110 C. for two hours and at 150 C. for six hours under 2 mm. pressure. At the end of this time, the product was an elastic adhesive resin which was soluble in alchohol, ethylene dichloride, benzene, and dioxane. tional five hours at 200-210 C. under 2 mm. pressure to give an amber, transparent thermoplastic resin. It was soluble in xylenol and in acetic acid but insoluble in ethanol, butanol, benzene, and ethylene dichloride.

Example 7 A mixture of 8.6 grams of decamethylenediamine and 10.0 grams of p-oarboxyethyl-Z-ethylhexaldehyde was heated for four hours at 130- 150 C. while a slow stream of nitrogen was passed through the melt. The pressure was reduced to 2 mm. and the temperature raised to 210 C. and

held there for two hours. The product was a transparent yellow elastic resin. It was soluble in xylenol and in acetic acid but was insoluble in benezene, ethanol, and ethylene dichloride.

Example 8 The resin was heated for an addibenezene, ethylene dichloride, butanol, and acetic acid.

Example 9 A. mixture of 3.44 parts of decamethylenediamine and 6.68 parts of an aldehydo-acid having the formula:

CH3(CH2) 3-CsI-I'1(CHO) -CH==CH(CH2) 7COOH was heated in a stream of nitrogen for one hour at 103-107 C. and then for one and one-half hours at 200210 C. The system was then evacuated to a pressure of .3 mm. of mercury, and the reaction mixture was heated for one hundred thirty minutes at 210-216 C. while dry nitrogen was passed through the melt by means of a capillary inlet tube. The product was an orange-red, slightly tacky resin. The hot melt could be drawn into elastic fibers. The resin was soluble in butanol, ethylene dichloride, and toluene.

The aldehydo-acid used above is obtainable by heating acrolein in an autoclave in an atmosphere of hydrogen with eleostearic acid at 190 210 C. and is a pale-yellow oil which boils at 220-230 C./3 mm.

Example 10 A mixture of 3.68 parts of benzidine and 4.00 parts of 2-(p-carboxyethyl)-2-ethylhexaldehyde was heated for six hours at 205-215 C. while a slow stream of nitrogen was passed through the melt. The system was then evacuated to a pressure of 4 mm. of mercury and heated for an additional three and one-half hours at 205215 C. while nitrogen was passed through the melt by means of a capillary inlet tube. The product was a dark, fusible, tack-free resin. It was soluble in ethanol, butanol, and ethylene dichloride but was insoluble in benzene.

Example 11 A mixture of 5.40 parts of p-phenylenediamine and 10.00 parts of 2-(fl-carboxyethyl)-2-ethylhexaldehyde was heated for four hours at 205- 215 C. while a slow stream of nitrogen was passed through the melt. The system was then evacuated to a pressure of 3 mm. of mercury and heated an additional three hours at 205-215 C. while nitrogen was passed through the melt by means of a capillary inlet tube. The product was a dark fusible resin, soluble in acetic acid and in xylenol, slightl soluble in n-butanol and in ethylene dichloride, and insoluble in benzene and in alcohol.

Example 12 A mixture of 0.82 part of tetramethylenediamine and 1.86 parts of 2-(p-carboxyethyD-2- ethylhexaldehyde was heated in a slow stream of nitrogen While the temperature was gradually increased during three hours from to 200 C. The system was evacuated and heated an additional three hours at 200-260 C. at 1 mm. pressure. The product was a transparent orange resin.

Example 13 A mixture of 6.52 parts of methyl aldehydo stearate (obtained by the addition of carbon monoxide and hydrogen to methyl oleate) and 3.44 parts of decamethylenediamine was heated in nitrogen for one hour at C., for two hours at 215 C., and finally for eight hours at 220- 250 C. at 1 mm. pressure. The product was a which comprises condensing by heating together an aldehydo non-aromatic carboxylic acid, having one aldehydo and one carboxylic group as the sole reacting functional groups thereof and having two to sixteen carbon atoms in a chain between said functional groups, and a polyamine having as the sole reacting functional groups thereof hydrogen-bearing amine groups, at least one of which is a primary amine group, said amine groups being separated by a group containing at least four carbon atoms, the amount of said polyamine being reacted providing a proportion of a said primary amine group which is chemically equivalent to the aldehydo group of said carboxylic acid.

2. A process for preparing resinous materials which comprises reacting by heating together (a) a carboxylic compound selected from the group consisting of aldehydo non-aromatic carboxylic acids, having one aldehydo and one carboxyl group as the sole reacting functional groups thereof and having two to sixteen carbon atoms in a chain between said functional groups, and esters of said acids and a saturated aliphatic alcohol of one to eight carbon atoms and (b) a polyamine having as the sole reacting functional groups thereof hydrogen-bearing amine groups, at least one of which is a primary amine group, said amine groups being separated by a group containing at least four carbon atoms, the amount of said polyamine being reacted providing a proets) portion of a said primary amine group which is chemically equivalent to the aldehydo group of said carboxylic compound.

3. A process for preparing resinous materials which comprises condensing by heating together an aldehydo non-aromatic carboxylic acid and an aliphatic diprimary amine, said acidhaving one aldehydo and one carboxylic group as the sole reacting functionalgroups thereof and having two to sixteen carbon atoms in a chain between said functional groups, the aldehydo and carboxylic groups being separated by a chain of at least two carbon atoms, said amine having twoprimary amine groups as the sole reacting functional groups thereof and an alkylene chain of four to ten carbon atoms, the two amine groups being separated by at least four intervening carbon atoms and the amount of said amine being substantially chemically equivalent to said acid.

4. A process for preparing resinous materials which comprises reacting by heating together below 300 C. one molar proportion of deca methylene diamine-and one molar proportion of 2- (beta-carboxyethyl) -2-ethy1butyraldehyde.

5. A process for preparing resinous materials which comprises reacting by heating together below 300 C. one molar proportion of hexamethyl: ene diamine and one molar proportion of 2-(betacarboxyethyl) -2-ethylbutyraldehyde.

A product obtained by the process of claim 2.

'7. The product obtained by the process of claim 4.

8. The product obtained by the process of claim 5.

HERMAN A. BRUSON. WARREN D. NIEDERHAUSER.

REFERENCES CITED The following references are of record in the Bruson et al Feb. 22, 1944 

